Insecticidal compositions



2,941,922 I I INSECTICIDAL COMPOSITIONS Philip Gerolt, Herne Bay, England, assignoi to Shell Oil Company, a corporation of Delaware No Drawing. Filed May 6,1957, Ser. No. 657,062 Claims priority, application Great Britain May 195.6

11 Glaims. Cl. 167-42) 7 This invention relates to insecticidal compositions for use on sorptive surfaces and'mor'e specifically to halogenated polycyclic insecticides such as aldrin, dieldrin, isodrin and endrin which manifest surprisingly superior residual insecticidaltoxieity when admixed with an asphaltite such as gilsonite.

In the past, insecticidal mixtures have been sprayed or otherwise deposited on surfaces possessing sorpt'ive properties. It has been found, however, that these mixtures soon lose their insecticidal potency. In hot, dry, tropical and subtropical areas, where the interior mud walls of native huts are treated with insecticidal sprays to eliminate disease carrying insects diminution o'f potency is particularly acute. The need for an insecticidal composition evidencing extended residual toxicity when applied to sorptive surfaces'such as mudw alls has consequently become increasingly'manifest; Yet in spite of intensive research in the past this-urgent need has remained an- It is, consequently, the principal object of the present invention to provide insecticidal compositions which manifest'extended residual activity when placed on sorptive surfaces such as mud walls. 1

Another object of the present invention is to provide a method for formulating insecticidal compositions which manifest extended residual activity.

the migration of the insecticidal componentfrom the sur- United States Patent O face to the inner layers of the treated material where its contact insecticidal action can no' longer be effectively manifested. In. this manner, the residues of both volatile vand non volatile insecticides losetheir activity j'l he cause of this migration is not yetknown, Tbut-appea-rs to be connected with some power of the sorpt-i-ve material to attract the molecules of the insecticidal substance. This diminution of insecticidal potency by migration is not to be cb'nfused with diminution due to evaporation of insecticideshaving relatively high vapor pressures. The

diflierence between these two phenomena will be immediately obvious to those well versed in the art. t

0f recent years aldrin, endrin, isodrin, and particularly dieldrin have been increasingly used as the active "ingie-i dient in residual insecticidal sprays. Aldrin is the name of a product consisting essentially of 1,2,3,4,10,10-hexachloro 'l,4,4a,-5,8,*8a 'hexahydro 1,4,5',8a--, endo, exodimethanonaphtha'lene. Isodrin is the name of aproduct consisting essentially of the stereoisomer of al'drin'having u the endo, endo configuration. Dieldrin 'isthe Iflamflgffl product consistingc's'sentially of the 6,7-epoxy derivative exerted by the sorptive material.

Patented June 21, 1960 of aldriu, and endrin is the name of a produc'tjconsisti'ng essentially of the endo, jendo 'isomerof dieldrin. These insecticides .havelb'een' found to rapidly lose their insecticidal potency when applied to, absorbent .or adsorbent it has now been dis'covered that the deactivation of residueso fdieldrin;as1well as other halogenated polycyclic insecticides when applied to the surfaces ofmaterial with sorptive properties, can be substantially .inhibited if the insecticidal substance is in intimate contact or intimate admixture withan asphaltite such as gilsonite.

The attraction .for the molecules of insecticidal substance exerted by the asphaltite is very much greater than that The insecticidal substance is consequently held on the surface of the'treated material where it can continueto exert its insecticidal activity. 7

This discovery is of "the greatest importance whenfconsidered with reference to the current campaign to eliminate-malaria carrying mosquitos in tropical areas. This campaign aims at breaking the chain of malaria transmission by spraying dwelling houses in malarial zones with insecticide. In order to break this chain of transmission,

however, the active insecticidal agent must remain active for an extended time period. Though therhalogenated polycyclic insecticides such as dieldrin evidence satisfactory residual toxicity for some purposes, they are unsatisfactory when prolonged residual toxicity fo'n sorbent surfaces is essential. The discovery that the intim ate admixtureg particularly the solid solutions, of the present invention-maintain residual insecticidal toxicity for very extended periods of time, even when applied to these-surfaces, consequently fills an urgent need in an altogether unique yet highly efficient manner.

Asphaltites are generally defined asnaturally occurring -aspha'lt like substances, characterized by their high fusing points '(over' 230 -F.). They are grouped into three I classes; gilsonite; glance pitch and grahamite. Because all are derived from petroleum, these classes tend to merge'zintoon'e another. Generally spealcing, however, gil'sonite may be defined as an asphalt-ite which has a specific gravity of approximately l.'03'l.'l"0 at 77 1- a softening point of about 230-350 F. and-a carbon "cent min'the vi 'n'ity'of 10-20%.

Gilsonite is further classified into'a stand ar'd-g'rade and a select grade both *of' 'which may be employed for the purposes ofthe present invention. Gil'so'nite select is abrownish blaek, naturally-occurring asphaltite having a soften-iug point of 27=5"-F. Gilsonite standard has a softening point of shear-"34.0" F. L l'riti-mate contact metween the insecticidal substance and' the gilsonite maybe eifected lay grinding the two components together. Contact" between the insecticidal substance and the Ig'ilsoniteis considerably improved "with corresponding increase in the residual toxi'city'if a solution of two components in an organic solvent is evaporated to dryness. The solid residue thus ob itained is subsequently powdered; greatest improvement in residual toxicity is obtained however, when the insecticidal substance and the gilsonite are brought into intimate contact in a homogeneous molten mixture of the two components. A solid solution can be formed by so melting the components.

. The intimate mixtures of insecticide and gilsonite thus formed arevastly superior to the intimate mixtures made y grinding or by evaporation from an organic solven and-constitute the preferred compositions of th s invention, The present invention encompasses both satu- -.rated, supersaturatedand unsaturated mutual solid solutions of .a halogenated 'polyillclic insecticide such as .di-

eldnin and an 'asphal't'ite such as gilsonite. Of course it fwiltbe readily understoodthat other "intimate homogene- 5 ing of formulations shown above as compared to a "conventional wetting powder:

Test of dieldrin wettable powders made from high ratio gilsonite melts Dieldrln applied at rate of 25 mg. per sq. ft. on 9 cm. mud blocks} Percent Mortallty fiense Flies Sam 1e Melt Ratio I Percent Y Num er Dieldrln: Gllsonlte Gilsonlte in w. p. Fresh 1 -2 a 1 1 '2 Deposit day days, week weeks Standard 50% 'wettable powders 100 85 7 14 12 62.5:37.5 30 100 99 84 100 60 62.5237. 30 100 100 92 100 100 62.5137 30 100 98 94 100 100 55.6:44. 40 100 100 100 100 80 57.1142. 30 100 95 91 97 100 44.4255. 50 100 99 98 '98 100 42.9:57. 40 100 99 99 100 100 33.3:66. V 60 99 1'00 100 100 100 62.5:37. 30. 3 100 '100 98 i DQuirik-gmoled, except where noted (cooled by immersion of container 11 ry ce b Intermediate-cooled (cooled at room temperature).

Slow-cooled (cooled over steam bath at 80100 C).

One very excellent dieldrin-gilsonite formulation consists of:

e Percent by weight Technical dieldr'in 50.5 Gilsonite selec 30.0 A'ttaclay 9.4 Urea 5 V 2.1 Duponol ME dry 1.0 Mar'asperse CB V 6.0 Sodium tripolyphosphate 1.0

Total 100.0

Another formulation of promise consists of:

Percent by Weight (100% purity) technical dieldrin -2 50.5 Gilsonite select 24.9 Attaclay 15.8 Urea 1 .8 Marasp'erse CB 6.0 -Duponol :ME dry e 1.0 .Sodium tripolyphosphate 1.0

Total N n M. 100.0

The toxicity of dieldrin and ;dieldrin-gilsonite wettable j-powd'ers encompassed by the present invention is further evidenced by the following table. All samples tested contained urea, Duponol ME dry, Marasperse CB and sodium tripolyphosphate.

Toxicity tests of 50% dieldrin and dieldrin-gilsonite wettable powders [Dleldrtn applied at 25 mg. per sq. ft. on 9 cm. mud panels] The gilsonite,dleldrin, Marasperse CB and Attaclay were pow dared, hammer-and-air-milled.

A comparison was made of the behavior of dieldringilsonite physical mixtures and dieldrin-gilsonite melts,

and diluents added.

b'oth containing equal amounts of the 'twolcomponents,

together with wetting and suspending agents but .no fillers.

The following table shows the results obtained with these 7 formulations. The dosage was .25 mg. dieldrin/sq. ft.

Percentage knockdown and 24-hour mortality (percent) of Muscadomestica after 30 seconds exposure to residues of dieldrin/gilsonite, 50:50, on mud panels Number of Hours After Experimental Form- Age of Exposure ula'tlons of Dieldrinl Residues Gilsonite, 50:50

2 hours..." 9 51 65 93 100 100 2 weeks 14' 33 71 86 100 100 Physical mixture n. 1 month..." 0 1O 29 39 58 84 100 2months 6' 12 14 35 38 50 100 3 months-.. 0 0 5 2O 30 50 100 2 hours 15 50 91 '97 97 97 2 weeks- 29 42 82 95 100 Melt 1 month..-" 9 21 53 85 100 100 2 months. 11 36 7'2 92 97 100 100 3 months-" 0 0 19 49' 91 98 100 'The dieldrin and gllsonite were mixed, hammer-and-air-milled b The dieldrin and gllsonite were melted, diluents added and hammerand air milled.

The insecticidal activity of the formulations ofthis invention before and after storage is evidenced by the following experiments;

A formulation containing 50% dieldrin, 30% gilsonire by weight (melt) and a 20% by weight mixture of fullers earth and china clay in a 1:1 proportion together with \ve'tting agents was retested after storage for a period of two months at 20 C. The results, presented in the following table, clearly 'show that storage at 20 'C. for two months, did not afliect the biological performance of this formulation on inud underthe experimental conditions.

Percentage knockdown ond-24-hour mortality of Musca domestica after 30 seconds exposure to residues of dieldrin/gilsonitc/ filler (before and after storage) on mud panels In another experiment an air-milled product containing 50% by weight dieldrin, 25% by weight gilsonite (melt) and 25% by weight Microcel and wetting agent was tested under the following storage conditions:

a. One week at 20 C.

b. One day at 55 C. (tropical storage test) and one week at 20 C.

0. Seven weeks at 20 C. I

d. Three weeks at 20 C. and four weeks at 30 C.

e. Three weeks at 20 C. and four weeks at 40 C.

At the end of the storage period samples of the formulations were sprayed on mud panels (25 mg. dieldrin/sq. ft.), which were then tested on houseflies at successive intervals as indicated in the following table. This specific formulation appears to work best at temperatures not in excess of 30 C. Other formulations have been found to maintain their biological activity for extended periods oi time at temperature well in excess of 30 C.

Percentage knockdown and 24-hour mortality of Musca domestica after 30 seconds exposure to residues of dieldrin/gilsonite/filler (stored under various temperature conditions on mud panels) [Formulationz dieldrin/Gilsouite/microeel 50:25:25 (air-milled)] Number of Hours After Exposure Storage Age of Conditions Residue 2 h0us 6g 14)? 100 "1.) 180 s wee rs 2 94 0 1 at 20 1 mouth." 6 2s 59 81 90 97 100 2 months 0 7 31 74 98 100 100 100 100 1 day at 55 C 0 0 0 29 29 54 100 1 week at 20 0.... 0 0 6 29 43 60 100 0 0 0 0 6 94 81 100 100 2 a a 33131" a 0 0 1o 50 74 9'1 100 95 100 100 3 weeks at 20 C." 0 31 72 90 97 100 100 4 weeks at 30 C. 0 O 23 55 70 00 0 0 44 68 S5 100 98 100 100 3 weeks at, C 0 0 0 4 11 39 100 4 weeks 211540" 0... 1 monthmn 0 0 0 0 9 22 90 2 months 0 0 0 O l) U 75 It will be readily understood that other diluents and surface active agents than those specifically named may be successfully employed in the insecticidal compositions of the present invention. Thus among the many diluents and carriers which may be successfully employed are the diatomites such as diatomaceous earth, calcium limes, calcites, dolomites, gypsum, mica, talc, pyrophyllites, members of the montmorillonoid group such as bentonite, kaolinites, attapulgites as well as other naturally occurring and synthetic diluents and carriers. It will also be evident that the extent of the dilution may vary considerably Without departing from the scope of the invention and that the invention is not limited to 50% Wettable powders. Moreover, the specific quantities of insecticide and asphaltite employed are only to be construed as limited by the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An insecticidal composition comprising an intimate homogeneous mixture of a chlorinated polycyclic compound selccted from the group consisting of aldrin, isodrin, dieldrin and endrin, and an asphaltite, the ratio of said asphaltite to said polycyclic compound ranging between 1:2 and 5:1.

2. An insecticidal composition comprising an intimate homogeneous mixture of dieldrin and an asphaltite, the

ratio of said asphaltite to said dieldrin ranging between 1:2 and 5:1.

3. An insecticidal composition comprising an intimate homogeneous mixture of endrin and an asphaltite, the ratio of said asphaltite to said endrin ranging between 1:2 and 5:1'.

4. An insecticidal composition comprising an intimate homogeneous mixture of isodrin and an asphaltite, the ratio of said asphaltite to said isodrin ranging between 1:2 and 5:1.

5. An insecticidal composition comprising an intimate homogeneous mixture of aldrin and an asphaltite, the ratio of said asphaltite to said aldrin ranging between 1:2 and 5 1.

6. An insecticidal composition comprising a solid solution of a chlorinated polycyclic compound selected from the group consisting of aldrin, isodrin, dieldrin and endrin, and gilsonite, the ratio of said gilsonite to said polycyclic compound ranging between 1:2 and 5:1.

7. An insecticidal composition comprising a solid solution of dieldrin and gilsonite, the ratio of said gilsonite to said dieldrin ranging between 1:2 and 5:1.

8. An insecticidal composition comprising a solid solution of endrin and gilsonite, the ratio of said gilsonite to said endrin ranging between 1:2 and 5 1.

9. An insecticidal composition comprising a solid solution of isodrin and gilsonite, the ratio of said gilsonite to said isodrin ranging between 1:2 and 5: 1.

10. 'An insecticidal composition comprising a solid solution of aldrin and gilsonite, the ratio of said gilsonite to said aldrin ranging between 1:2 and 5:1.

11. An insecticidal composition comprising a solid s0 lution of dieldrin and 5% to by Weight gilsonite, the ratio of gilsonite to dieldrin ranging between 1:2 and 5: 1.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Handbook of Aldrin, Dieldrin and Endrin, Shell Chem. Corp, 1954 (122 pp.), esp. pp. 23-28, 51-59 and 71-75. 

1. AN INSECTICIDAL COMPOSITION COMPRISING AN INTIMATE HOMOGENEOUS MIXTURE OF A CHLORINATED POLYCYCLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDRIN, ISODRIN, DIELDRIN AND ENDRIN, AND AN ASPHALTITE, THE RATIO OF SAID ASPHALTITE TO SAID POLYCYCLIC COMPOUND RANGING BETWEEN 1:2 AND 5:1. 